Composition for preparing electroconductive resin comprising an unsaturated urethane and phosphoric or sulfonic unsaturated ester

ABSTRACT

A composition for preparing an electroconductive resin with excellent properties of electrical conductivity, resistance to organic solvent, mechanical strength, adhesiveness and film forming property, and said composition consisting of at least: ALKYLENE PHOSPHORIC ESTERS, ALKYLENE PHOSPHATE ESTERS, ALKYLENE SULFONIC ESTERS OR ALKYLENE SULFONATE ESTERS OF ACRYLIC ACID OR METHACRYLIC ACID; AND A POLYFUNCTIONAL UNSATURATED COMPOUND HAVING TWO TO FOUR POLYMERIZABLE ETHYLENICALLY UNSATURATED GROUPS; AND IF NECESSARY, FURTHER CONTAINING A POLYMERIC MATERIAL AS A FILM-FORMING AGENT AND/OR A POLYMERIZABLE ETHYLENICALLY UNSATURATED COMPOUND; AND/OR A POLYMERIZATION INITIATOR.

United States Patent [191 Juna et a1.

[4 1 Feb. 18, 1975 [73] Assignee: Kansai Paint C0,, Ltd.,

Amagasaki-shi, Hyogo-ken, Japan {22] Filed: Nov. 24, 1971 [21] Appl. No.: 201,991

[30] Foreign Application Priority Data Nov. 25, 1970 Japan 45-103328 Dec. 25, 1970 Japan 45-118132 [52] U.S. Cl.260/77.5 CR, 117/93.1 OH, 117/161 C, 117/161 UZ, 117/161 R, ll7/l6l UN,

260/17 R, 260/304 R, 260/304 N,'260/32.8

N, 260/328 R, 260/332 R, 260/793 M.

260/78 UA, 260/785 BB, 260/785 UA [51] Int. Cl... C08g 22/00, C08g 22/06, C08g 22/16 [58] Field of Search 252/500; 260/775 R, 77.5 CR, 260/775 AP, 77.5

[56] References Cited UNITED STATES PATENTS 2,748,050 5/1956 Shearer et al 260/308 X 10/1966 l/l97l Bailey et a1. 260/895 R X Hausslein ct al. 260/77.5 CR

OTHER PUBLICATIONS Chem. Abstracts, Vol. 74, 1971, 143380N. Gotoda et al., Effective Date 1970.

Primary ExaminerHoward E. Schain Attorney, Agent, or Firm-Ostrolenk.Faber Gerb & Soffen [57] ABSTRACT A composition for preparing an electroconductive resin with excellent properties of electrical conductivity, resistance to organic solvent, mechanical strength, adhesiveness and film forming property, and said composition consisting of at least:

alkylene phosphoric esters, alkylene phosphate esters, alkylene sulfonic esters or alkylene sulfonate esters of acrylic acid or methacrylic acid; and

a polyfunctional unsaturated compound having two to four polymerizable ethylenically unsaturated groups;

and if necessary, further containing a polymeric material as a film-forming agent and/or a polymerizable ethylenically unsaturated compound; and/or a polymerization initiator.

11 Claims, No Drawings COMPOSITION FOR PREPARING ELECTROCONDUCTIVE RESIN COMPRISING AN UNSATURATED URETHANE AND PHOSPHORIC OR SULFONIC UNSATURATED ESTER This invention relates to compositions for preparing electroconductive resins.

Further, the invention relates to the compositions used to prepare novel electroconductive resins each having good electric conductivity, resistance to organic solvent, mechanical properties, adhesive property and film forming property.

A superior electroconductive resin has long been looked for in order to prepare good electroconductive paper. In the prior art, a method is well known in which a resin consisting of polymerized vinyl benzyl quaternary ammonium compound is dispersible in water, and thereafter the medium, water, is vaporized to obtain an electroconductive film on a substrate. However, selection of reaction conditions to obtain reaction products free from gelation is very difficult, and therefore the obtained products are very expensive. Furthermore, the obtained electroconductive film has very low electric conductivity, such as l X 10 to l X 10 ohms in the surface specific resistance and l X 10 to l X 10 ohmscm in the volume specific resistance in air having a relative humidity of about 50%. Still more, the electrical conductivity of the product is largely dependent upon change of the relative humidity. For example the surface specific resistance of such electroconductive film in air having a relative humidity of about 30% becomes 1 X l to l X ohms which is as much as 10 to a 100 times as large as the aforementioned value. Further, resistance to organic solvent and mechanical properties are inferior because such film is formed by means of the evaporation of the solvent used.

Accordingly, the object of the present invention is to remove the above-mentioned disadvantages of the prior known electroconductive resin. In other words, the object of the invention is primarily to provide a composition for preparing electroconductive resins with good electrical conductivity. Further, the object of the invention is to provide a composition from which a novel and superior electroconductive resin can be prepared very easily and economically, in which resistance of organic solvent, mechanical properties and adhesive property of the obtained film therefrom are excellent, and the time required for the film forming step is short.

As the result of the extensive studies on the abovementioned objects, the inventors of the present invention have accomplished the objects of the invention.

That is, the composition of the present invention essentially comprises (A) alkylene phosphoric esters, alkylene phosphate esters, alkylene sulfonic esters or alkylenc sulfonate esters of acrylic acid or methacrylic acid, and (B) polyfunctional unsaturated compound having two or more polymerizahle ethylenically unsaturated groups. The composition ol the present invention further comprises, (C) polymeric materials as a filmforming agent which is miscible with the abovementioncd (A) and (B) components, (D) polymerizable ethylenically unsaturated compounds and/or (E) polymerization initiators.

The alkylene phosphoric ester or alkylene phosphate ester of acrylic acid or methacrylic acid is represented by the following general formula:

and the alkylene sulfonic ester or alkylene sulfonate ester of acrylic acid or methacrylic acid is represented by the following general formula:

The alkylene phosphoric esters of acrylic acid and methacrylic acid which may be used for the composi' tion of the present invention are, for example, phosphoric ethylene acrylate, phosphoric ethylene methacrylate, phosphoric trimethylene acrylate, phosphoric isopropylene methacrylate, phosphoric trimethylene methacrylate, phosphoric tetramethylene methacrylate, phosphoric l-chloromethylethylene methacrylate, phosphoric-bis-(ethylene acrylate), phosphoric-bis- (ethylene methacrylate), phosphoric-bis-(trimethylene acrylate), phosphoric-bis-(isopropylene methacrylate), phosphoric-bis-(trimethylene methacrylate), phosphoric-bis-(tetramethylene acrylate), and phosphoricbis-(tetramethylene methacrylate). If the number of carbon atoms in the alkylene groups of the above compounds is more than four, the reactivity of the ethylenically unsaturated group of the ester is lowered, and the film forming property may almost be lost.

As for the alkylene sulfonic esters of acrylic acid and methacrylic acid which can be used for the composition of the present invention, for example, sulfomethylene acrylate, sulfoethylene acrylate, sulfoethylene methacrylate, sulfotrimethylene acrylate, sulfoisopropylene acrylate, sulfotrimethylene methacrylate, sulfotetramethylene acrylate, sulfobutylene methacrylate, and sulfopentamethylene acrylate are noted. lf the number of carbon atoms in the alkylene groups of the above compounds is more than five, the reactivity of the ethylenically unsaturated group of the esters is lowered and the film-forming property may also be lost.

The alkylene phosphate esters can be prepared by neutralizing the alkylene phosphoric esters with inorganic or organic bases. In like manner, the alkylene sulfonate ester may be obtained by neutralizing the alkylene sulfonic esters with inorganic or organic bases.

The above-described neutralization can be carried out by using monovalent metallic bases, for example,

sodium hydroxide, lithium hydroxide, potassium hydroxide and silver perchlorate.

Further, ammonia, 'alphat ic monoamines and cyclic monoamines can be used for the neutralization. For example, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-butylamine, monoethanolamine, diethanolamine and triethanolamine as aliphatic monoamines and pyridine, aniline, morpholine, and piperidiene as aromatic monoamines, are exemplified. These bases can be used alone as a mixture.

This neutralization may be carried out by means of the known method. The amount of the abovementioned esters to be used for the composition is in the range of 5 to 95% by weight, and preferably in the range 'of to 70% by weight.

As for the polyfunctional unsaturated compounds each having two or more polymerizable ethylenically unsaturated groups which can be used for the composition of the present invention, unsaturated urethane compounds each having two or more ethylenically unsaturated groups which are prepared from ethylenically unsaturated compounds each having one hydroxyl group and polyisocyanate compounds each having two or three isocyanate groups or addition products of polyisocyanate compounds each having two or three of isocyanate groups with polyhydric alcohols each having two to four of hydroxyl groups; unsaturated polyesters which are prepared from ethylenically unsaturated compounds each having one carboxyl group and polyhydric alcohols each having two to four hydroxyl groups; N,N-alkylene-bis-(acryl amides), in which alkylcnc group is methylene or ethylene, N,N-alkylenebis-(methacryl amides) in which alkylene group is methylene or ethylene, dimaleimide and diallyl esters of dicarboxylic acids are exemplified.

It the above-mentioned polyfunctional compounds are not used in the composition, the composition cannot be polymerized, and accordingly, the electroconductive film cannot be obtained. The amount of the polyfunctional unsaturated compounds used for the composition of the present invention may be in the range of 5 to 95% by weight, and preferably in the range of 30 to 90% by weight.

The ethylenically unsaturated compounds each having one hydroxyl group for the preparation of the above-mentioned unsaturated urethane compounds used for the composition of the invention are allyl alcohol methallyl alcohol and N-methylol acrylamide, and those which are represented by the following general formula: 1

in which each of R and R are hydrogen or methyl group respectively. The above compounds'are hydroxyalkyl esters of acrylic acid or methacrylic acid, for example, one member or a mixture of two or-more of the group comprising of 2-hydroxyethyl acrylate, 2- hydroxypropyl acrylate, -2-hydroxyethyl methacrylate and Z-hydroxypropyl methacrylate.

As for the polyisocyanate compounds, one member or a mixture of two or more of the group comprising, for example, tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, naphthylenel,5-diisocyanate, 3,3-dimethyldiphenyl- 4,4-diisocyanate and polymethylene polyphenylene isocyanate, can be used.

' The isocyanate compounds (e.g. hexamethylene diisocyanate) in which two isocyanate groups react at the same or nearer the same rate cause the gelation by cross-linking reaction of diisocyanate compounds with polyhydric alcohols. Therefore, suchdiiso'cyanate compounds must be used by mixing other polyisocyanate (e.g. tolylene diisocyanate, polymethylene polyphenylene isocyanate) in which one of the isocyanate groups reacts with a hydroxyl group at a much greater rate than does its other isocyanate group.

i The addition reaction of hydroxyl group with isocyanate group may be carried out by means of well-known methods, in which the materials are used in such ratio that 1.0 equivalent of the isocyanate group is caused to react with 0.67 to 1.0 equivalent of the hydroxyl group of the hydroxyalkyl esters.

Further, as for the polyhydric alcohols, one member or a mixture of two or more of the group comprising, for example, ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, triethylene glycol, neopentyl glycol, propylene glycol, polypropylene glycol, trimethylol propane, glycerin andpentaerythritol can beused. These polyhydric alcohols improve the'film-forming property, and, in addition, they control the intermolecular cross-linking density to improve the mechanical property of the film formed. The reaction ofthese alcohols with isocyanates may be carried out by means of the known methods.

In the case of preparing the unsaturated urethane compounds by using the polyhydric alcohols, the materials are used in such ratio that 1.0 equivalent of hydroxyl group of polyhydric alcohols is caused to react with more than 1.0 equivalent of the isocyanate group, and then the residual isocyanate groups is caused to react with the same equivalent of the hydroxyl group of the hydroxyalkyl esters.

As for the ethylenically unsaturated compounds having one earboxyl group for obtaining the unsaturated esters which are used for the composition of the invention, one member or a mixture of two or more of the group comprising, for example, acrylic acid, methacrylic acid, a-chloroacrylic acid and a-bromoacrylic acid can be used. Meanwhile, as for the polyhydric alcohols each having two to four of hydroxyl groups for the preparation of the esters, one member or a mixture of two or more of the group comprising, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, neopentyl glycol, propylene glycol and polypropylene glycol as dihydric alcohols, trimethylol propane and glycerin as trihydric alcohols, and pentaerythritol as a tetrahydric alcohol, can be used. The esterification may be carried out by means of the wellknown method, in which the materials are used in such ratio that 1 equivalent of the carboxyl group is caused to react with l to 2 equivalents of the hydroxyl group.

The number of carbon atoms of the alkylene groups contained in N,N-alkylene bis (acrylamides) or N,N'-

alkylene bis (methaerylamides) as the polyfunctional .unsaturated compound is l to 2, and one or a mixture of two or more of the group comprising, for example, N,N-methylene bis (acrylamide), N,N-methylene bis (methacrylamide), N,N'-ethylene bis (acrylamide) and N,N'-ethylene bis (methacrylamide) may be used.

Further, the allyl compounds as the polyfunctional unsaturated compound for the composition of the invention may be one member or a mixture of two or more of the group comprising, for example, diallyl phthalate, diallyl maleate and diallyl succinate.

The mixture of the compounds of the abovementioned groups can also be used as the polyfunctional unsaturated compounds of the invention.

Furthermore, polymeric materials as a film-forming agent can be used for the preparation of the composition of the invention in order to improve the filmforming property and appliability. These polymeric materials must be miscible with the alkylene phosphoric esters. alkylene phosphate esters, alkylene sulfonic esters or alkylene sulfonate esters, and the polyfunctional unsaturated compounds, and are used for the composition in the range of to 130% by weight, preferably to 110% by weight, based on total weight of alkylene phosphoric esters, alkylene phosphate esters, alkylene sulfonic esters or alkylene sulfonate esters and polyfunctional unsaturated compounds. These polymeric materials are effective to promote the physical properties of the electroconductive film, especially when are applied on paper or plastic film as a substrate. As such polymeric materials, for example, there can be used one member or a mixture of two or more of the group comprising polyvinyl alcohol, N-vinylpyridine copolymers, butyral resins, vinyl acetate copolymers, acrylic resin such as acrylic acid copolymers, methacrylic acid copolymers and Z-hydroxyethyl acrylate copolymers, cellulose derivatives such as cellulose acetate, cellulose acetate phthalate, ethyl cellulose acetate phthalate, ethyl cellulose, methyl cellulose and cellulose acetate -N,N'-di-n-butyl-aminohydroxy propyl ether.

Furthermore, ethylenically unsaturated compounds can be used for the preparation of the composition of the invention in order to improve the appliability, filmforniing property and other film properties such as electric conductivity and flexibility of film formed. These unsaturated compounds must be miscible with the polyfunctional unsaturated compounds and the polymeric materials, and are used for the composition in the amount of not more than 40% by weight, preferably not more than 30% by weight based on the total weight of alkylene phosphoric esters, alkylene phosphate esters, alkylene sulfonic esters or alkylene sulfate ester and the polyfunctional unsaturated compounds. These ethylenically unsaturated compounds are effective to promote the cross-linking reaction of the polyfunctional unsaturated compounds with the esters of alkylene phosphoric esters, alkylene phosphate esters, alkylene sulfonic esters or alkylene sulfonate esters of acrylic acid or methacrylic acid. The ethylenically unsaturated compounds which are liquid or solid at the room temperature can be used. As such compounds, for example, one member or a mixture of two or more of the group comprising the vinyl monomers represented by the following three general formulas:

l. styrene and its derivatives R "CaCH l ca e-c0012 in which R is hydrogen or methyl group and R is hydrogen, alkyl group having 1 to 16 carbon atoms, hy-

droxyalkyl group having 2 to 3 carbon atoms, glycidyl group and dialkylamino alkyl group in which R is alkylene group having I to 2 carbon atoms and R is an alkyl group of l to 2 carbon atoms,)

and 3 vinylidene compounds in which R is hydrogen or methyl group and R is nitrile group, carbamoyl group, N-methylolcarbamoyl group, alkylether-N-methylolcarbamoyl group (CONl-lCl-l OR; in which R is alkyl group having I to 4 carbon atoms) or acetoxy group.

Examples of vinyl monomers (l) are styrene, vinyl toluene, Z-methyl styrene and chlorostyrene.

Examples of vinyl monomers (2) are acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylatc, Z-ethyl hexyl acrylate, 2-cthyl hexyl mcthacrylate, octyl acrylate, octyl methacrylate, lauryl methacrylate, 2- hydroxyethyl acrylate, 2hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, Z-hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, dimethylaminomethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethylaminoethyl methacrylate.

Examples of vinyl monomers (3) are acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, ethylether-N-methylol acrylamide, ethylether-N- methylol methacrylamide, butylether-N-methylol acrylamide, propylether-N-methylol methacrylamide and vinyl acetate.

In the polymerization reaction of the composition of the invention, if the polymerization is initiated by means of electron beam and ionizing radiation which have sufficient energy to initiate the polymerization reaction, the polymerization initiator is not necessary. However, in such case the polymerization initiator can he used without any trouble. In case the polymerization initiator is used for the composition of the invention, the amount thereof may be not more than 10% by weight, and preferably not more than 5% by weight based on the total'weight of alkylene phosphonic esters, alkylene phosphate esters, alkylene sulfonic esters or alkylene sulfonate esters and the polyfunctional unsaturated compounds.

When the electroconductive resin film is formed from the composition of the invention by using h'eat rays, the ordinary free radical polymerization initiators, for example, organic peroxides (e.g. benzoyl peroxide,

and mechanical properties of the obtained resin are excellent compared with those of the ordinary solvent hydrogen peroxide, methyl ethyl ketone peroxide and evaporation-drying type resins. Further, the film can be di-tert-butyl Peroxide) and organic aZO-COmPOUHdS cured in a short period of time and the adhesive prop- -gazobisisobutyro nitrile and a-azobis- 1 erty of the film is also superior. Still further, the compocyclohexane Carbonitrlle) are used, and when the sition ofthe invention can be made by using several relgy Source is actinic y the n ry Ph atively low' molecular weight compounds, and theresensitizers such as the organic peroxides (e.g. benzoyl l0 fore, there is no fear of gelation, and such low molecuperoxide, methyl ethyl ketone peroxide, hydrogen perlar weight materials can be produced easily. Accord- OXide and di-tert-butyl P organic azoingly the cost of the composition of the invention is compounds (e.g. azobisisobutyronitrile and a-azobis-lvery low. Furthermore, the composition of the invencyclohexane carbonitrile), organic sulfur compounds tion consists of relatively low molecular weight com- (e.g. diphenyl disulfide, tetramethylthiuram monosulpounds and therefore, resins with wide variety of propfide, tetramethylthiuram disulfide and di-tert-butyl die rties'can be obtained by selecting the amounts and sulfide), organic carbonyl compounds (e.g. benzoin, kinds of the components, and the electric conductivity benzoin ethyl ether, benzoin butyl ether, benzoin pheof the resin can be made uniform. 1n the preparation of nyl ether, anthraquinone,biacetyl, benzophenone, acethe electroconductive resin from the composition of tophenone and 9-bromoacetophenone) and metallic the invention, if the actinic ray is irradiated through a salts (e.g. uranyl nitrate, silver perchlorate and ferric patterned mask, the cured pattern having the electric chloride) can be used alone or in a mixture of two or conductivity can be formed by removing the unirmore. These polymerization initiators are usually used radiated portion after the irradiation. in the range of 0.1 to 10.0% by weight, preferably 0.5 The electroconductive resin obtained from the comto 5.0% by weight, based onthe total weight ofalkylene position of the invention is also entirely different in phosphonic esters, alkylene phosphate esters, alkylene structure from those in the prior art. Therefore. the efsulfonic esters or alkylene sulfonate esters and the fects of the resin are far better in several points which polyfunctional unsaturated compounds. have never been expected. The composition of the When the electroconductive resin is produced from present invention is especially suitable for coating mathe composition ofthe present invention, it is sufficient terial to provide electroconductive paper as well as only to expose the composition to heat rays, actinic many other uses. rays or ionizing radiations. ln heating, the temperature In the following, the objects and features of the presmay be in the range of 50 to 150C, and if it is lower ent invention will become more apparent in accorthan about 50C, the cross-linking reaction cannot be dance with the Examples, which are intended as merely brought about, and the film-foamed is obtained by illustrative and in no way restrictive of the invention. heating in the tmeperature of higher than about 150C. In case the actinic ray is irradiated to form the electroconductive resin, the composition is irradiated with the EXAMPLES l 60 actinic ray in the range of 2500 to 6000 angstroms Mercury was placed in each Petri dish (10 cm in diwave-length. Further, the resin can be obtained in a 40 ameter and 1.5 m in d p to f rm a layer of m rshort period of time by the application of ionizing radicury, and the compositions of Exmaples l to 60 as ations such as gamma rays, electron beam, etc. Accordshown in Table 1, (a) to (f) were poured on each meringly, the polymerization of the composition of the incury layer, then each dish was covered and stood still vention can be initiated by means of various methods. for about one hour so as to remove the foams. In case The electric resistance ofthe resin obtained by crosssolvents were used in the compositions, the covers of linking the composition is l X 10 to 1 X 10 ohms in the dishes were then taken off and the dishes were furthe volume specific resistance and l X 10 to 1 X 10 ther stood still at the room temperature in order to reohms.cm in the surface specific resistance in air having move the solvents. the relative humidity of and this value is from 50 The samples thus obtained were cured by the applione-hundredth to one-hundred thousandth compared cation of actinic rays or heat rays, then the thicknesses with those ofthe prior known electroconductive resins. of the films, surface specific resistances and volume In addition, the electric resistance of the resin of the inspecific resistances were measured, the results of which vention is not as dependent upon the changes of the relare shown in Table 2, (a) to (c), inclusive. ative humidity, that is, the value in air having the rela- In the curing step by irradiating actinic rays, a 400 W tivc humidity of 30% is twice or at the most about 5 high-pressure mercury lamp H4OOP (made by Tokyo times that at 50%. Shibaura Electric Co., Ltd.) was used at a distance of In the preparation of the electroconductive resin 50 cm from the surface layer of the composition, and from the composition of the present invention, the the irradiation was continued until each composition cross-linking reaction is caused by the exposure of the was completely cured.

TABLE 1 (21) Example A B"2 I) F. Solvent 1 PhQSIncr-Cl (7.5g) AUT-4(J()F. Acetone (5.0g) 2 Phosmcr-Cl (1.5g) AUT1()()0E (8.5g) llcnzoin ethyl Acetone (5.0g)

ether ((1. lg) 3 Phosmer-Cl (1.5g) AUT-400E (6.5g) Benzoin (0.1g) Acetone (5.0g) Phosmer-Cl (3.5g) AUT4400E (5.0g) Tetramethyl thiuram Acetone (5.0g)

monosulfidc (0.1g)

TABLE 1 (d) Contmued Example A" B D E" Solvent 37 SEM (l.7$g) AUT-400E (325g) Benzoin (0.05g) Acetone (5.0g) 38 SEM (l.25g) AUT-2000E (3.75g) Tetramethyl Acetone (5.0g)

thiuram monosulfide (005g) 39 SEM (2.50g) AUT-2000E (2.50g) Benzoin ethyl Acetone (5.0g)

ether (005g) 40 SEM (5.00g) AUT-400E (12.003) Ethyl acrylate (3.00g) 4l SEM (|0.00g) AUT-40OE (8.00g) Butyl Benzoin ethyl acrylate ether (020g) (2.00g) 42 SEM (15.00g) AUX-400E (4.00g) Ethyl Benzophenone methacrylate (0.20g)

Table l (e) Example A B D E Solvent 43 SEM (500g) AUT-IOOOE (12.00g) Ethyl acrylate Benzoyl peroxide (3.00g) (020g) 44 SEM (2.50g) NK-4G (250g) Benzoin ethyl Acetone (5.0g)

"ether (0.05g) 45 SEM (l.25g) NK-l4G (3.75g) Methylethyl Acetone (5.0g)

' ketone peroxide (0.05g) 46 SEM (600g) N.N'-methylene Acrylic acid Benzoin ethyl hismcthucrylumide (2.40g) ether (01 (9.603) 47 SEA (3.00g) AUT-60OE (12.00g) Ethyl ucrylate Benzoin ethyl (2.0g) ether (0.2g) Methyl methacrylate (3.0g) 48 SEM-TEA (5.0g) AUT-lOOOE (12.0g) Ethyl acrylate Benzoin (0.2g)

. (3.0g) 49 SBA (5.0g) NK-l4G (12.0g) Vinyl acetate Tetramethyl (3.0g) thiuram monosulfide (0.2g) 50 SEM (3.0g) Diallyl Vinyl acetate Azobisisobutyrophthalate (3.4g) nitrile (0.2g) 13.6g) 51 Silver AUT-NPG (8.0g) Butyl acrylate Anthraquinone salt of (1.0g) 0.2g) SEM (100g) 52 Potassium AUT-NPG (10.0g) Butyl acrylate Anthraquinone salt of (2.0g) (0.2g) SEM (8.0g)

TABLE 1 (f) Example A B" C" D D Solvent 53 SEM (2.5g) AUT-IOOOE (3.5g) CAP (4.0g) Benzoin Methyl ethyl ethyl ether ketone (0- 3) 54 Potassium AUT-400E (1.0g) EC (6.0g) Benzoin Methyl ethyl salt of AUP-600E (1.0g) (0.1g) ketone (40g) SEM (1.0g) SEM (3.0g) 55 Phosphoric NK-23G (3.0g) VMCH (3.0g) Benzoin MEK (20g) tetramethylene ethyl methacrylate (4.0g) ether Acetone (20g) (0.1) 56 SEM (1.0g) AUT-IOOOE (2.0g) BXL (5.0g) Benzoin Acetone (40g) AUT-NPG (2.0g) g) 57 SBM (3.5g) AUT-IOOOE (0.5g) NVP (5.0g) Anthra- Acetone (20g) NK-l4G (1.0g) quinone methyl alcohol (0.2g) (20g) 58 Phosphoric NK-l4G (1.0g) CABP (4.0g) Benzoin Acetone (40g) bis (ethylene NVP (1.0g) (0.1g) acrylate (5.0g) 59 SEM (1.0g) NK-MG (2.5g) AC (2.0g) Benzoin Acetone (10g) Silver salt of HEMA (2.5g) ethyl me0th)anol (l g SEM (1.0g) ether Triethyl phosphoric ethylene ncrylntc (Ulg) M) Potassium NK-MU (0.5g) (AP (5.5g) ncryl- Benzoin Acetone (10g Silll of nmidc (0.1g) phosmcr-M (4.0g) (1.5g)

are alkylene phosphoric esters, alkylene phosphate esters, alkylene sulfonic esters or alkylene sulfonate es saturated compounds, the details of which are also shown in the following Table 3.

(*4) The compounds as disclosed in the column E are polymerization initiators.

ters as stated in the initial part of this specification. 5 i i g dlsclosed m w g Each formula or formation of these compounds is furare F Creme 9 ymenc matfena e S of which are also shown in the following Table 3. ther listed in the following Table 3.

6) The surface specific resistances (ohm) and the 2) The compolfnds as dlscloseq m the Column B volume specific resistances (ohm.cm) as shown in are the aforementioned poly functional unsaturated 10 Table 2 (a) to Table 2 (C) were measured in acc0r compounds each of which having two to four of polydance with ASTM by using electrode Type merizable ethylenically unsaturated groups. The details (made by Takeda Riken, Japan) for measuring of these compounds are listed also in the following the ultra high electric resistance and an ammeter Table (made by Yokokawa Electric Works, Limited, Japan). (*3) The compounds as disclosed in the column D The measurements were carried out at a temperature are the aforementioned polymerizable ethylenically unof C and a relative humidity of TABLE 3 (a) Abbreviation chemical Name Structural formula etc.

Column A (3113 on Phosmer-M Phosphoric ethylene CH2=C-C-O-CH2CH2O-1| =O methactylate g h 1 9X3 P osmer-C Phosphoric-1-chloromethyl ethylene methacrylate CHI-C |C| 0 CH2 (EH CHZCJ Phosphoric tetramethylene (EH3 9H methacrylate CH =Cl 3-OnH CH -CH CH O =O Silver salt of Phosmer-M Potassium salt of Phosmer-M-IEA Phosphoric ethylene acrylate Obtained by neutralizing Phosmer-M with silver TABLE 3 (b) Abbreviation Chemical Name Structural formual etc.

a CH

- Phosphoric bisethylene 3 methacrylate CH =C-| fOCI-I -ClI -O OH P cu 1 o Q CH :C|I-O-CH CH SEM 2-sulfoethylene methacrylate SEA 2-sulfoethylene acrylate SEM-TEA Triethylamirie salt of 2-sulfoethylene methacrylate SBA 4-sulfobutylene acrylate SBM 4-sulfobutylene methacrylate a. r,,i .l s r TABLE 3 (c) Silver salt of SEA SEM Ohtained by neutralizing SEA with using silver perchlorate Abbreviation Chemical Name Composition etc.

Column 3 W 7' A A f Unsaturated urethane compound consisting of:

2-hydroxyethyl methacrylate mols, tolylene diisocyanate 2 mole, and polyethylene glycol (m.w.=40 0) 1 mol.

' Alli-600E Unsaturated urethane compound consisting of:

2-hydroxyethyl methacrylate mols, tolylene diisocyanate 2 mole, and

polyethylene glycol (m.w.=600) 1 mol.

E Unsaturated urethane compound consisting of:

r 2-hydroxyethyl methacrylate 2 mols,

xylene diisocyanate 2 mole, and polyethylene glycol (m.w.=600) 1 mol.

AUP-GOOE Unsaturated urethane compound consisting of:

2-hydroxyethyl methacrylate 2 mols, diphenylmethane diisocyanate 2 mole, and polyethylene glycol (m.w. =600) 1 mol.

AUT-lOOOE Unsaturated urethane compound consisting of:

2-hydroxyethyl methacrylate 2 mols, tolylene diisocyanate 2 mole, and polyethylene glycol (m.w.=l000) 1 mol.

TABLE 3 (d) Abbreviation Chemical Name Composition etc.

AUT-ZOODE Unsaturated urethane compound consisting of:

2-hydroxyethyl methacrylate 2 mols, tolylene diisocyanate 2 mole, and

polyethylene glycol (m.w.=2000) 1 mol.

AUT-NPG Unsaturated urethane compound consisting of:

Z-hydroxyethyl methacrylate 2 mols, tolylene diisocyanate 2 mols, and neopentyl glycol 1 mol.

NK-l4G Unsaturated ester consisting of:

polyethylene glycol (m.w.==630) 1 mol, and methacrylic acid 2 mols.

NK-23G Unsaturated ester consisting of:

polyethylene glycol (rn.w.=l000) 1 mol, and methacrylic acid 2 mols.

AUX-400E Unsaturated urethane compound consisting of:

Z-hydroxyethyl methacrylate 2 molsl xylylene diisocyanate 2 mole, and polyethylene glycol (m.w.=400) 1 mol.

NK-4G Unsaturated ester consisting of:

polyethylene glycol (m.w.=200) 1 mol, and methacrylic acid 2 mole.

- TABLE 3 (e) Abbreviation Chemical Name Structural formula etc. 1

Column C I H O SEA Sulfoethylene acrylate 19 TABLE 3 (f) hhbr o viation Chemical Name or Composition etc.

Ch? Cellulose acetate phthalate 3C Ethyl cellulose VMCH Trade name: Vinyl chloride-vinyl acetate copolymer manufactured by Sekisul Chemical Co. Ltd. in Japan.

.' BX-L Trade name: Butyral resin manufactured by Sekisui Chemical Co. Ltd.

in Japan.

NVP Copolymer of N-vinyl pyridine/Butyl methacrylate/Vinyl acetate I 50/25/25 mp Cellulose acetate -N,N-din-butylaminohydroxy propyl ether.

Ac Copolymer of Acrylic acid/Methyl methacrylate 50/50 HEMA Copolymer of 2hydroxye'thylac\rylate/Methyl' acrylate/Butyl acrylate 50/20/30 EXAMPLES 61 7i Glass plates were adhered with polyester films (Tetoron Trade name) and further provided with rubber-made frames. The compositions as disclosed in Table 4 are poured into the frames, respectively. Then, each of the compositions was irradiated with one M rad dose of electron beam which had an energy of 250 KeV and had the beam-density of 50 aA/cm at the surface of the composition. The results of the measurements on the thicknesses, surface specific resistances and volume specific resistances, which were carried out in same manner as the former Examples, are shown in the following Table 4.

In Table 4, the abbreviations for the components of the compositions are the same as those in the foregoing Continued ()rlg as the photosensitizcr, and

Acetone was mixed well, and poured on the mercury layers in Petri dishes (10 cm in diameter and 1.5 cm in depth) like those in the foregoing Examples 1 to 60. The foams and the solvent in the composition were then removed.

Thereafter, the actinic rays were irradiated to the above samples in the same manner as in the foregoing Examples l to 60 for 5 minutes. Each electric resistance was measured in air having the following respective relative humidities (20%, 50% and 72.2%), in

Table 3. which the temperature was kept at 20C, and the result TABLE 4 Composition Electric Resistance Ex. A B C Film Surface Volume Thickness Specific Specific Resistance Resistance (ohm) (ohmcm) 6i Phosmcr Cl I (3.5g) AUT-OE (5.2g) Ethyl acrylate (13g) 0.l0 2.7Xl0 63x10 62 PhosmerCl (5.0g) AUT-400E (4.0g) Ethyl acrylate (l.0g) 0J2 l18 l0-" l.2 l0" (i3 Phosmcr-M (5.0g) AUT-400E (4.0g) Ethyl acrylate (L03) 0.l0 6.0Xl0 2.4Xl0

o4 Phosmcr-Cl (3.5g) NK-MG (5.2g) Vinyl acetate (13g) 0.11 8.3Xl0 3.3 10

(15 Phosmcr-(l (5.0g) NK-l4(i (4.0g) Vinyl acetate (1.0g) 0.18 3i5XlO 2.5Xl0" (so Phosmer-M (3.5g) NK-l4G (512g) Vinyl acetate (l.3g) 0.ll 6.4 l0 l.9 (l0-" (17 Phosmer-M (5.0g) NK-MG (4.0g) Vinyl acetate (l.0g) 0.l2 2.3Xl0 8.7Xl0

as Phosmcr-M (2.5g) AUT-400E (3.2g) Ethyl acrylatc (0.8g) 0.16 2.1 t0 5.1 10

NK-l4G (2.0g) Vinyl acetate (0.5g)

69 SEM (0.3g) AUT-400E (l 36g) Ethyl acrylate (034g) 0.15 4.2Xl0 3.9 l0

70 SEM (01g) AUT-400E (1.52g) Ethyl acrylate (033g) 0J9 l.2 l() 2,7Xl0

71 SEM (0.3g) NK-l4G (1.36g) Vinyl acetate (034g) 0.22 3.8Xl0 2.7Xl0

EXAMPLE 72 of which is shown in the following Table 5. The thick- A composition consisting of: Pl1ost11cr-M 5.( Al iltlfltlli 51);: (both aforementioned),

nesses of the formed films were 0.87 mm.

Resistance (ohm-cm) Controlling of the relative humidities was carried out through the following methods.

a. Relative humidity: 20%

The Petri dish was placed in a desiccator which contained a saturated aqueous solution of CH COOK (potassium acetate).

h. Relative humidity: 50%

The sample was left intact in the laboratory wherein the relative humidity was 50% and the temperature was 20C.

c. Relative humidity: 92.2%

The samples was placed in a desiccator which contained a saturated aqueous solution of NH,Cl (ammonium chloride).

As will be understood from the above results, the electroconductive resin of the present invention is not susceptible to the change of the relative humidity, for

example, the electric resistance at RH. 50% is only two G lQ l R O in which R is hydrogen or a methyl group, R is an alkylene group having I to 4 carbon atoms, R is an alkylene group having 1 to 5 carbon atoms, and each of M and M is hydrogen, a monovalent metal, ammonium or monoamine, and

B. urethane unsaturated compound having at least two polymerizable ethylenically unsaturated groups, wherein said urethane unsaturated compound is the reaction product of an ethylenically unsaturated compound having one hydroxyl group and a polyisocyanate having two or three isocyanate groups or a polyisocyanate having two or three isocyanate groups and a polyhydric alcohol having two to four hydroxyl groups.

2. A composition as claimed in claim 1, in which said alkylene phosphoric ester of acrylic acid or methacrylic acid is a member selected from the group consisting of phosphoric ethylene acrylate, phosphoric ethylene methacrylate, phosphoric trimethylene acrylate, phosphoric isopropylene methacrylate, phosphoric trimethylene methacrylate, phosphoric tetramethylene methacrylate, phosphoric l-chloromethylcthylene methacryl ate. phosphoriohisiethylene ncrylatc phosphorichis (ethylene mclliucrylalc). phosphoric his (trimcthylcne aciylalc). phosphoric his (isopropylcuc methacrylate), phosphoric-bis-(trimethylene methacrylate), phosphoric-bis-(tetramethylene acrylate) and phosphoric bis-(tetramethylene methacrylate).

3. A composition as claimed in claim 1, in which said alkylene sulfonic ester of acrylic acid or methacrylic acid is a member selected from the group consisting of sulfomethylene acrylate, sulfoethylene acrylate, sulfoethylene methacrylate, sulfotrimethylene acrylate, sulfoisopropylene acrylate, sulfotrimethylene methacrylate, sulfotetramethylene acrylate, sulfobutylene methacrylate and sulfopentamethylene acrylate.

4. A composition as claimed in claim 1, in which said alkylene phosphate ester or alkylene sulfonate ester of acrylic acid or methacrylic acid is an ester prepared by neutralizing the alkylene phosphoric esters or the alkylene sulfonic ester of acrylic acid or methacrylic acid with inorganic or organic base.

5. A composition as claimed in claim 4, in which said inorganic base is at least one monovalent metallic base selected from the group consisting of sodium hydroxide, lithium hydroxide, potassium hydroxide and silver perchlorate.

6. A composition as claimed in claim 4, in which said organic base is at least one aliphatic or cyclic monoamine selected from the group consisting of monoethyl amine, dimethyl amine, trimethyl amine, monoethyl amine, diethyl amine, triethyl amine, n-butyl amine, monoethanol amine, diethanol amine, triethanol amine, pyridine, aniline, morpholine and piperidine.

7. A composition as claimed in claim 1, in which the amount of said ester is in the range of 5 to by 7 weight.

8. A composition as claimed in claim 1, in which said polyisocyanate compound having two or three isocyanate groups is at least one member selected from the group consisting of tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, naphthylene-l,5-diisocyanate, 3,3-dimethyldiphenyl- 4,4-diisocyanate and polymethylene polyphenylene isocyanate.

9. A composition as claimed in claim 1, in which said polyhydric alcohol having two to four hydroxyl groups is at least one member selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, propylene glycol, polypropylene glycol, trimethylol propane, glycerine and pentaerythritol.

10. A composition as claimed in claim 1, in which the ethylenically unsaturated compound having one hydroxyl group is a hydroxalkyl ester of acrylic or methacrylic acid, and in which said unsaturated urethane compound is the reaction product of 1.0 equivalent of the isocyanate group of the polyisocyanate compound with 0.67 to 1.0 equivalent of the hydroxyl group of the hydroxyalkyl ester, or the reaction product of 1.0 equivalent of the hydroxyl group of the polyhydric alcohol and more than 1.0 equivalent of the isocyanate group of the polyisocyanate compound and the same equivalent of the hydroxyl group of the hydroxyalkyl ester as the residual isocyanate groups.

11. The composition of claim 1 wherein said component (A) is phosphoric-l'chloromethyl ethylene methacrylate and wherein said polyfunctional unsaturated compound is an unsaturated urethane of ingredients comprising Z-hydroxyethyl methacrylatc, tolylene diisocyanalc and polyethylene glycol.

i i I i i 

1. AN ELECTROCONDUCTIVE COMPOSITION WHICH COMPRISES: A. AT LEAST ONE ALKYLENE PHOSPHORIC ESTER, ALKYLENE PHOSPHATE ESTER, ALKYLENE SULFONIC ESTER OR ALKYLENE SULFONATE ESTER OF ACRYLIC ACID OR METHACRYLIC ACID, REPRESENTED BY THE FOLLOWING FORMULAE:
 2. A composition as claimed in claim 1, in which said alkylene phosphoric ester of acrylic acid or methacrylic acid is a member selected from the group consisting of phosphoric ethylene acrylate, phosphoric ethylene methacrylate, phosphoric trimethylene acrylate, phosphoric isopropylene methacrylate, phosphoric trimethylene methacrylate, phosphoric tetramethylene methacrylate, phosphoric 1-chloromethylethylene methacrylate, phosphoric-bis-(ethylene acrylate), phosphoric-bis-(ethylene methacrylate), phosphoric-bis-(trimethylene acrylate), phosphoric bis-(isopropylene methacrylate), phosphoric-bis-(trimethylene methacrylate), phosphoric-bis-(tetramethylene acrylate) and phosphoric bis-(tetramethylene methacrylate).
 3. A composition as claimed in claim 1, in which said alkylene sulfonic ester of acrylic acid or methacrylic acid is a member selected from the group consisting of sulfomethylene acrylate, sulfoethylene acrylate, sulfoethylene methacrylate, sulfotrimethylene acrylate, sulfoisopropylene acrylate, sulfotrimethylene methacrylate, sulfotetramethylene acrylate, sulfobutylene methacrylate and sulfopentamethylene acrylate.
 4. A composition as claimed in claim 1, in which said alkylene phosphate ester or alkylene sulfonate ester of acrylic acid or methacrylic acid is an ester prepared by neutralizing the alkylene phosphoric esters or the alkylene sulfonic ester of acrylic acid or methacrylic acid with inorganic or organic base.
 5. A composition as claimed in claim 4, in which said inorganic base is at least one monovalent metallic base selected from the group consisting of sodium hydroxide, lithium hydroxide, potassium hydroxide and silver perchlorate.
 6. A composition as claimed in claim 4, in which said organic base is at least one aliphatic or cyclic monoamine selected from the group consisting of monoethyl amine, dimethyl amine, trimethyl amine, monoethyl amine, diethyl amine, triethyl amine, n-butyl amine, monoethanol amine, diethanol amine, triethanol amine, pyridine, aniline, morpholine and piperidine.
 7. A composition as claimed in claim 1, in which the amount of said ester is in the range of 5 to 95% by weight.
 8. A composition as claimed in claim 1, in which said polyisocyanate compound having two or three isocyanate groups is at least one member selected from the group consisting of tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, naphthylene-1,5-diisocyanate, 3,3''-dimethyldiphenyl-4,4''-diisocyanate and polymethylene polyphenylene isocyanate.
 9. A composition as claimed in claim 1, in which said polyhydric alcohol having two to four hydroxyl groups is at least one member selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, propylene glycol, polypropylene glycol, trimethylol propane, glycerine and pentaerythritol.
 10. A composition as claimed in claim 1, in which the ethylenically unsaturated compound having one hydroxyl group is a hydroxalkyl ester of acrylic or methacrylic acid, and in which said unsaturated urethane compound is the reaction product of 1.0 equivalent of the isocyanate group of the polyisocyanate compound with 0.67 to 1.0 equivalent of the hydroxyl grOup of the hydroxyalkyl ester, or the reaction product of 1.0 equivalent of the hydroxyl group of the polyhydric alcohol and more than 1.0 equivalent of the isocyanate group of the polyisocyanate compound and the same equivalent of the hydroxyl group of the hydroxyalkyl ester as the residual isocyanate groups.
 11. The composition of claim 1 wherein said component (A) is phosphoric-1-chloromethyl ethylene methacrylate and wherein said polyfunctional unsaturated compound is an unsaturated urethane of ingredients comprising 2-hydroxyethyl methacrylate, tolylene diisocyanate and polyethylene glycol. 